CN1073083C - Process for the preparation of aryl carbonates - Google Patents
Process for the preparation of aryl carbonates Download PDFInfo
- Publication number
- CN1073083C CN1073083C CN95108160A CN95108160A CN1073083C CN 1073083 C CN1073083 C CN 1073083C CN 95108160 A CN95108160 A CN 95108160A CN 95108160 A CN95108160 A CN 95108160A CN 1073083 C CN1073083 C CN 1073083C
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- CN
- China
- Prior art keywords
- gram
- acid
- salt
- monohydroxy compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 31
- -1 aryl carbonates Chemical class 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 150000002148 esters Chemical class 0.000 claims description 17
- 238000004438 BET method Methods 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 abstract 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- 230000035484 reaction time Effects 0.000 description 23
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 22
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000009466 transformation Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 150000001457 metallic cations Chemical class 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- BHSXLOMVDSFFHO-UHFFFAOYSA-N (3-ethylsulfanylphenyl)methanamine Chemical compound CCSC1=CC=CC(CN)=C1 BHSXLOMVDSFFHO-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 1
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- SGGPVBOWEPPPEH-UHFFFAOYSA-N [K].[Zr] Chemical compound [K].[Zr] SGGPVBOWEPPPEH-UHFFFAOYSA-N 0.000 description 1
- FKSZLDCMQZJMFN-UHFFFAOYSA-N [Mg].[Pb] Chemical compound [Mg].[Pb] FKSZLDCMQZJMFN-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- BJXXCWDIBHXWOH-UHFFFAOYSA-N barium(2+);oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ta+5].[Ta+5].[Ta+5].[Ta+5] BJXXCWDIBHXWOH-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- GKJROTAYDAJLGD-UHFFFAOYSA-N carbonyl dichloride;hydrochloride Chemical compound Cl.ClC(Cl)=O GKJROTAYDAJLGD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XJUNRGGMKUAPAP-UHFFFAOYSA-N dioxido(dioxo)molybdenum;lead(2+) Chemical compound [Pb+2].[O-][Mo]([O-])(=O)=O XJUNRGGMKUAPAP-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical class CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 1
- JNQQEOHHHGGZCY-UHFFFAOYSA-N lithium;oxygen(2-);tantalum(5+) Chemical compound [Li+].[O-2].[O-2].[O-2].[Ta+5] JNQQEOHHHGGZCY-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- RPEUFVJJAJYJSS-UHFFFAOYSA-N zinc;oxido(dioxo)niobium Chemical compound [Zn+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O RPEUFVJJAJYJSS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Carbonates with aromatic ester groups are prepared by reaction of aromatic monohydroxy compounds with phosgene or with chloroformic acid esters of aromatic monohydroxy compounds, whereby operations are carried out at a temperature in the range of 50 DEG to 450 DEG C. and at a pressure in the range of 0.05 to 20 bar in the presence of metallates of the elements of groups IIIa, IVa, Va, VIa, IIIb, IVb, Vb, VIb, VIIb, and VIII of the Mendeleev periodic system as heterogeneous catalysts.
Description
The metal acid-salt (metallates) that the present invention relates to III a, IV a, V a, VI a, III b, IV b, V b, VI b, VII b and VIII family element in the Mendeleev chart is a heterogeneous catalyst, make the chloro-formic ester reaction of aromatic monohydroxy compound and phosgene or aromatic monohydroxy compound, and remove hydrogenchloride, thereby preparation has the method for the carbonic ether of aromatics ester group.
Carbonic ether with aromatics ester group is suitable for being used for being equipped with polycarbonate according to the melt transesterification legal system, preparation phenyl urethanes, or the intermediates of medicine and plant protection aspect active substance.
Know that aryl carbonates can be made through phase interface phosgenation reaction (Schotten-Baumann reaction) by aromatic hydroxy compound.The shortcoming of this method is to use solvent and sodium hydroxide solution, because the part saponification reaction may take place for phosgene or chloro-formic ester under the effect at alkali aqueous solution under some occasion.In all cases, all can produce a large amount of by product sodium-chlor.In addition, also need to carry out solvent recuperation.
Therefore, US-A-2,837,555 have proposed without solvent with the condensation reaction of halogenation tetramethylammonium as catalyzer.But the amount of required catalyzer is quite big.In order to reach the speed of reaction with economic implications, catalyst consumption is a benchmark with the consumption of phenol, generally needs 5-7%; Temperature of reaction is 180 ℃-210 ℃, and has the danger that heat-labile halogenation tetramethylammonium is decomposed.In addition, the method that must wash with water is subsequently removed catalyzer, and the result makes it reclaim difficulty more.In addition, used up phosgene is many more than required stoichiometry.
According to another kind of method (US-A-3,234,263), diaryl carbonate makes the phenyl chloroformate heating as catalyzer with tertiary nitrogen alkali with a large amount of alkali (alkaline earth) metallic compound.But this method has shortcoming, promptly in order to reach the receptible economically reaction times, must adopt high temperature, and catalyzer, must be partly dissolved as alkali (alkaline earth) metallic compound.In the method, the phosgene that originally uses has half with CO
2Form loses.In addition, chloro-formic ester must be synthetic in other operation in advance.
According to US-A-2,362,865 method, diaryl carbonate is to be made through phosgenation reaction by aromatic hydroxy compound under metal titanium, iron, zinc and tin or its solubility salt form, particularly muriate and phenates existence.Although productive rate is very high, be difficult to catalyzer is separated from product.In distillation procedure, must consider impurity, downgrade and yield losses that the thermolysis owing to the volatilization to a certain degree of described compound and described compound causes.
Therefore, use heterogeneous insoluble catalyzer seemingly proper, in fact this catalyzer helps the aftertreatment of reaction mixture.Some of the recommendations were also once arranged in this respect.For example, according to the report of EP-A-516 355, the special recommendation aluminum trifluoride optionally is used in it such as on the aluminosilicate carrier.But because the processing of fluorine or hydrofluoric acid is relatively more difficult, thus the synthetic very complexity of aluminum fluoride, and also relatively more expensive.In addition, narrated the metal-salt that can be used as according on the porous support of catalyst for reaction of the present invention among the WO 91/06526.As from test examples as can be seen, only in gas phase, phenol could carry out totally continuous phosgenation reaction on this catalyzer, still, the temperature of reaction that this has relatively high expectations, and the danger that exists responsive chloro-formic ester to decompose.Obviously, the phosgenation reaction that carries out phenol with described catalyzer in liquid phase is impracticable, because the liquid phenol of heat can come out active catalyst component.
Therefore, the objective of the invention is to develop the easier effective heterogeneous catalyst that obtains.
Have now found that, the metal acid-salt of the III a in the Mendeleev chart, IV a, V a, VI a, III b, IV b, V b, VI b, VII b and VIII family element, for example titanate is the excellent catalysts of phosgene or chloro-formic ester and aromatic hydroxy compound reaction.This is wondrous especially and beyond thought, because according to the report of prior art WO 91/06526, mention metal, is suitable as stable inert support material as the oxide compound of titanium and zirconium.
Therefore, the objective of the invention is method by the cyancarbonic acid ester prepared in reaction aryl carbonates of aromatic monohydroxy compound and phosgene or aromatic monohydroxy compound, it is characterized in that this reaction is 50-450 ℃ temperature range, randomly under the pressure at 0.05-20 crust, and in the presence of the metal acid-salt as Mendeleev chart III a, IV a, V a, VI a, III b, IV b, V b, VI b, VII b and the VIII family element of heterogeneous catalyst, carry out.
The advantage that the inventive method is very big is that catalyzer is easy to separate, and residual without any impurity in the crude reaction product.Thereby simplified aftertreatment greatly.
The aromatic monohydroxy compound that is applicable to the inventive method is the compound shown in the following formula:
Ar
1Ar in-OH (I) formula
1Represent phenyl, naphthyl, anthryl, phenanthryl, 2,3-indanyl, tetralyl or one are contained 1 of being selected among N, O and the S or 2 heteroatomic 5-or 6-unit aromatic heterocyclic group, wherein said carbocyclic ring or heterocyclic group can be by 1 or 2 substituting groups, as the C of straight or branched
1-C
4The C of alkyl, straight or branched
1-C
4Alkoxyl group replaces, and these alkyl and alkoxyl group can be replaced by phenyl, cyano group and halogen (as F, Cl, Br), thereby this heterocyclic group can be coupled together by the condensed benzene nucleus.
The example of aromatic monohydroxy compound shown in the formula I has: phenol, adjacent-,-, p-Cresol, adjacent-,-, right-isopropyl benzene phenol, the phenol that corresponding halogen and alkoxyl group replace, as para-chlorophenol, p methoxy phenol, naphthalene, anthracene and luxuriant and rich with fragrance monohydroxy compound, and 4-pyridone and hydroxyquinoline.The preferential phenol that uses optional replacement, and phenol itself is most preferred.
Both can also can carry out according to method of the present invention with phosgene with the chloro-formic ester of aromatic monohydroxy compound.If carry out with phosgene, then initial generation chloro-formic ester, this ester reacts with the extra aromatic monohydroxy compound that is present in the reaction mixture then, thereby changes into diaryl carbonate.
With chloro-formic ester and aromatic monohydroxy compound is that raw material can make symmetry or asymmetric carbonic ether.
The aromatic chloroformate that is applicable to the inventive method is the compound shown in the following formula II:
Ar
1-OCOCl (Ⅱ)
Ar in the formula
1Definition and formula I in provide identical.
The metal acid-salt that in meaning scope of the present invention, is suitable for be below the compound shown in the logical formula III:
AxByOz (III) is wherein:
A represents monovalence, divalence and/or trivalent metal cation,
B represents trivalent, tetravalence, pentavalent and/or sexivalent metallic cation,
X represents the number of 1-4,
Y represents 1 or 2 number,
Z represents 3,6,7 or 9 number.
The example of the metallic cation A that can mention has:
The monovalence metallic cation, as: Li, Na, K, Rb, Cs, Cu, Ag and Tl,
Divalent metal, as: Be, Mg, Ca, Sr, Ba, Zn, Hg, Sn, Pb,
Fe,Mn,Co,Ni,
Trivalent metal cation, as: B, Al, Ga, Y, Tl, Bi, Fe, Mn, Co, Cr,
V, Mo, Na wherein, K, Be, Mg, Ca, Ba, Fe, Ni, Zn, Al, Pb, Cr, V and Mo are reasonable.Na, K, Mg, Ca, Ba, Fe, Pb, Ni and Zn are good especially.
The example of the metallic cation B that can mention has:
Trivalent metal cation is as Sc, Y, and Cr, Mn, Fe and Ga,
The tetravalent metal positively charged ion is as Ti, Zr, and Hf, V, Nb, Mo, Ru, Os, Re, Ir,
Sn and Pb,
The pentavalent metallic cation is as V, Nb, and Ta, Re, Ru, Os, Rh, Ir, Sb and Bi,
The sexavalence metallic cation is as Mo, W and Te,
Ti wherein, Zr, Nb, Ta, V, Mo, W and Sn are reasonable, Ti, Zr, Nb and Ta are good especially.
One or more metallic cations A or metallic cation B also can occur by different valence mumbers in metal acid-salt together.The metal acid-salt that is particularly suitable for as heterogeneous catalyst is the metal acid-salt with uhligite and pyrochlore constitution.
They can exist with the crystallized form of various forms.They can be all or part of unbodied.
The production method of this metal acid-salt and source thereof or this compound can referring to, the chemical technology complete works of Kirk-Othmer (the Encyclopedia of ChemicalTechnology) third edition for example, the 20th volume, below 410 pages, 22 volumes, 656 pages, 23 volumes, below 153 pages, 19 volumes, below 651 pages, 13 volumes, 768 pages, below 782 pages, New York, 1969/1983; The technical chemistry complete works of Ullmann ＇ s (Encyclopediaof Industrial Chemistry) the 5th edition, the 17th volume, 431 pages, Weinheim1966; And EP0547791,0575745.
No matter be the metal acid-salt that obtains from natural resource, promptly various mineral substance, as ilmenite or uhligite, or the metal acid-salt of synthetic, as from precursor, for example the metal acid-salt that makes of metal-salt, metal oxide and metal alkoxide all is suitable for.
The metal acid-salt that can be used for the inventive method better is a titanate, zirconate, niobate and tantalate, lithium titanate for example, sodium titanate, potassium titanate, barium titanate, strontium titanate, calcium titanate (uhligite with the false cube form of oblique crystal exists), magnesium titanate (existing) with rhombus, aluminium titanates (tieillite with α and β type exists), cadmium titanate (existing) with quadrature and cubic structure, cobalt titanate (existing) with rhombus and cube form, iron titanate (existing) with ilmenite or pseudobrookite, manganese titanate (existing) with hexagon and cube form, nickel titanate, zinc titanate (spinel form), lead titanate (orthogonal angle vertebra shape), lithium zirconate, sodium zirconate, potassium zirconium, barium zirconate, calcium zirconate, strontium zirconate, zirconic acid iron, the zirconic acid lanthanum, the zirconic acid yttrium, sodium columbate, potassium niobate, calcium niobate, niobic acid magnesium, zinc niobate, niobic acid iron (existing) with niobite, niobic acid nickel, lead niobate, tantalic acid sodium, potassium tantalate, lead tantanate, magnesium stannate, calcium wolframate, barium wolframate, zinc molybdate, lead molybdate, and blended metal acid-salt, as niobic acid magnesium lead, niobic acid ferromanganese, the plumbous and tantalic acid zinc barium of tantalic acid magnesium.
Metal acid-salt in meaning scope of the present invention can use with dried forms, part dried forms or hydrate forms.
Because the result of mixed metal hydroxides and metal oxide/oxyhydroxide continuously dehydrating (roasting) under the temperature more than 80-1200 ℃, the metal acid-salt of generating portion dehydration originally, this salt still contains a great deal of hydroxyl, along with the carrying out that dewaters can become anhydrous metal acid-salt.Different with the character of starting raw material oxyhydroxide or oxide/hydroxide, may be in roasting process by the various forms of above-mentioned metal acid-salt.
The BET surface-area of metal acid-salt is preferably 0.1-500m
2/ g, more preferably 0.5-450m
2/ g is preferably 1-400m
2/ g.Acid, neutral and alkaline metal acid-salt all can use.
Catalyzer can, for example use, and after reaction with powder or molding form, for example separated by filtration, deposition or method such as centrifugal.If be arranged to fixed bed, then metal acid-salt better is with the molding form, uses as forms such as sphere, garden cylindricality, bar-shaped, hollow garden cylindricality, annulars.
When operating with suspended catalyst in stirred vessel or bubble-plate column, the amount that the usefulness of metal acid-salt catalyzer is put with used monohydroxy compound is a benchmark, can be 0.5-100% (weight), is preferably 5-100% (weight), more preferably 5-50% (weight).
Adverse current or and flow in the operate continuously, or the spray on fixed bed catalyst is mutually or in the operate continuously in the gas phase, catalyst loading is per hour (that is 0.1-20gg, of 0.1-20 gram aromatic hydroxy compound/every gram catalyzer
-1H
-1), be preferably 0.2-10gg
-1H
-1, 0.2-5gg more preferably
-1H
-1Can reuse needn't purifying for used metal acid-salt in batch test, uses identical raw material simultaneously.If raw material changes, then metal acid-salt can be used inert solvent temporarily, as following those solvents of mentioning for example as reaction medium, or use alcohols, as methyl alcohol, ethanol, Virahol or butanols, or extract, purify with the ester class or the acid amides of acetate, perhaps, purify with superheated vapour or air handling.
In operate continuously, used metal acid-salt can stop one long period in reactor.Can randomly feed superheated vapour when regenerating, randomly add little air (about 0.1-20% weight, with used quantity of steam is benchmark), temperature is 150-800 ℃, perhaps feed the diluent gas that contains 0.01-20% (weight) oxygen, as nitrogen or carbonic acid gas, perhaps singly using carbonic acid gas, temperature is 200-800 ℃.Preferred regeneration temperature is 150-700 ℃, is more preferably 200-600 ℃.
Method of the present invention 100-400 ℃ more fortunately, is better carried out in 100-350 ℃ temperature range at 50-450 ℃.When implementing method of the present invention, can change temperature within the limits prescribed, better be elevated temperature.
Method of the present invention is clung at 0.05-20, carries out under the 1-5 bar pressure more fortunately.
Can implement method of the present invention by solvent, spendable solvent for example has: aliphatic series and aromatic hydrocarbons, as the various isomer of pentane, hexane, octane, benzene, dimethylbenzene, diethylbenzene, alkylnaphthalene, biphenyl; Halohydrocarbon is as methylene dichloride, trieline etc.Method of the present invention both can also can be carried out in liquid phase in gas phase.
Method of the present invention better is to carry out in solution, for example, can be incorporated into the chloro-formic ester of phosgene or formula II in the suspension of metal acid-salt in the aromatic monohydroxy compound melt shown in the formula I, and after reaction is finished, isolate catalyzer by filtration or centrifugal means.
Present method can make phosgene and phenol evaporation and make this mixture by being arranged in the bulk catalyst bed in the pipe when carrying out in gas phase.
Another preferably synthetic example is in the bubble-plate column of an operate continuously or series connection bubble-plate column the chloro-formic ester shown in phosgene or phosgene-chlorine hydride mixed gas or the formula II to be passed in the melt of the aromatic monohydroxy compound shown in the formula I that is suspended with metal acid-salt with gas form.
Another preferred examples is a cocurrent process, wherein with the chloro-formic ester shown in aromatic monohydroxy compound photoreactive gas shown in the formula I or the formula II with and stream mode, for example be incorporated in the beds that is arranged in the pipe from the top, hydrogenchloride photoreactive gas product is then extracted out from the pipe bottom.
Another preferred embodiment with particularly advantageous result is to implement of the present invention reaction with reflux type at the spray quinoline in mutually, wherein the aromatic monohydroxy compound shown in the formula I is incorporated into the bed of metal acid-salt from the top with melt or solution form, and the logistics of phosgene or chloro-formic ester then is passed into the described liquid stream with reflux type from the below.Advantageously described example carries out in a vertical tubular reactor, and this reactor also can comprise central dividing plate, in order to improve the distribution of air-flow and liquid stream.Another preferred embodiment is a vapor phase process, and temperature of reaction is 150-450 ℃, better is 200-350 ℃, and pressure is the 0.05-20 crust, is preferably the 0.1-4 crust, more preferably the 0.1-3 crust.
In described method, pressure should change with the difference of temperature, makes each component be in the gas phase and can not condense upon in the catalyst filling.
The mol ratio of aromatic monohydroxy compound shown in the reactant formula I and phosgene is 0.5-8: 1, and better be 1.5-3: 1.Equivalent mol ratio in the case is 2: 1.
Aromatic monohydroxy compound is pressed 0.25-4 in the corresponding way: 1, and better 0.8-1.5: 1 mol ratio and chloro-formic ester reaction.In this case, mol ratio is 1: 1.
The thick product aromatic carbonate that makes with the heterogeneous catalyst method has been very pure usually, therefore can be used for multiple use with this form after removing residual chloride hydrogen or other volatile matter.For the application scenario that requirements at the higher level are arranged, if necessary, for example can adopting, method such as distillation or crystallization is further purified carbonic ether.
Example 1
In a flat flange form container that mobile buffer layer, gas dispersion agitator and reflux exchanger be housed, the powdery magnesium titanate of producing in 14.1 grams (account for phenol weight 10%) Bayer AG down in 140 ℃ with 0.75 mole/hour phosgene continuously processing 141 restrain (1.5 moles) phenol.React after 2 hours, phenol conversion is 36.4%, has only (58.3 gram) diphenyl carbonate to generate.Selectivity is greater than 99%.
Example 2
Repeat example 1 at 140 ℃ of powdery barium titanates of producing with 14.1 gram Aldrich companies.After 2 hour reaction times, phenol conversion is 31.6%, only generates diphenyl carbonate (50.1 gram).Selectivity is about 99%.
Example 3
Repeat example 1 at 140 ℃ of powdery lead titanate of producing with 14.1 gram Aldrich companies.After 2 hour reaction times, phenol conversion is 39.3%, only generates diphenyl carbonate (62.8 gram).Selectivity is greater than 99%.
Example 4
Repeat example 1 140 ℃ of powdery sodium titanate of producing with 14.1 gram Bayer AG.After 2 hour reaction times, phenol conversion is 21.5%, only generates diphenyl carbonate (34.1 gram).Selectivity is about 99%.
Example 5
Repeat example 1 at 140 ℃ of powdery calcium titanates of producing with 14.1 gram Aldrich companies.After 2 hour reaction times, phenol conversion is 35.4%, generates 51.6 gram diphenyl carbonates.Selectivity is about 91%.
Example 6
Repeat example 1 at 140 ℃ of powdery niobic acid magnesium of producing with 14.1 gram Starck companies.After 2 hour reaction times, phenol conversion is 16.0%, generates 2.1 gram phenyl chloroformates and 24.1 gram diphenyl carbonates.To the selectivity of carbonic ether greater than 99%.
Example 7
Repeat example 1 at 140 ℃ of powdery zinc niobates of producing with 14.1 gram Starck companies.After 2 hour reaction times, phenol conversion is 6.3%, generates 1.1 gram phenyl chloroformates and 9.2 gram diphenyl carbonates.To the selectivity of carbonic ether about 98%.
Example 8
Repeat example 1 at 140 ℃ of powdery niobic acid iron of producing with 14.1 gram Starck companies.After 2 hour reaction times, phenol conversion is 4.1%, generates 2.3 gram phenyl chloroformates and 4.2 gram diphenyl carbonates.To the selectivity of carbonic ether about 90%.
Example 9
Repeat example 1 at 140 ℃ of powdery tantalic acid zinc barium of producing with 14.1 gram Starck companies.After 2 hour reaction times, phenol conversion is 8.4%, generates 3.4 gram phenyl chloroformates and 10.8 gram diphenyl carbonates.To the selectivity of carbonic ether about 97%.
Example 10 (being used for contrast)
Repeat example 1 at 140 ℃, but do not add metal acid-salt.After 2 hour reaction times, phenol conversion is less than 0.2%.
Example 11
In the three-necked flask that thermometer and reflux exchanger are housed in the presence of powdery magnesium titanate that 0.94 gram (phenol weight 10%) Bayer AG produces, with the mixture heating up to 100 of 9.4 gram (0.10 mole) phenol and 15.7 gram (0.10 mole) phenyl chloroformates ℃.After 5 hour reaction times, recording the transformation efficiency that phenol conversion becomes diphenyl carbonate is 78.1%.The selectivity of carbonic ether is greater than 99%.
Example 12
Repeat example 11 at 120 ℃ with same catalyzer.After 2 hour reaction times, it is 88.3% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 13
Repeat example 11 at 140 ℃ with same catalyzer.After 0.5 hour reaction times, it is 45.5% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 14
Repeat example 11 at 160 ℃ with same catalyzer.After 1 hour reaction times, it is 97.8% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 15
Repeat example 11 at 160 ℃ of powdery barium titanates of producing with 0.94 gram Aldrich company.After 0.5 hour reaction times, it is 88.2% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 16
Repeat example 11 at 160 ℃ of lead titanate of producing with 0.94 gram Aldrich company.After 0.5 hour reaction times, it is 99.2% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 17
Repeat example 11 160 ℃ of powdery sodium titanate of producing with 0.94 gram Bayer AG.After 0.5 hour reaction times, it is 82.2% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 18
Repeat example 11 at 140 ℃ of powdery calcium titanates of producing with 0.94 gram Aldrich company.After 0.5 hour reaction times, it is 89.1% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 19
Repeat example 11 at 160 ℃ of powdery niobic acid magnesium of producing with 0.94 gram Starck company.After 3 hour reaction times, it is 64.7% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 20
Repeat example 11 at 160 ℃ of powdery zinc niobates of producing with 0.94 gram Starck company.After 6 hour reaction times, it is 28.6% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 21
Repeat example 11 at 160 ℃ of niobic acid iron of producing with 0.94 gram Starck company.After 5 hour reaction times, it is 65.5% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether about 97%.
Example 22
Repeat example 11 at 160 ℃ of powdery niobic acid nickel of producing with 0.94 gram Starck company.After 6 hour reaction times, it is 16.8% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether is greater than 99%.
Example 23
Repeat example 11 at 160 ℃ of powdery barium tantalate zinc of producing with 0.94 gram Starck company.After 4 hour reaction times, it is 74.9% that phenol conversion becomes the transformation efficiency of diphenyl carbonate.The selectivity of carbonic ether about 98%.
Claims (2)
1. the method for the chloro-formic ester prepared in reaction aryl carbonates by aromatic monohydroxy compound and phosgene or aromatic monohydroxy compound, it is characterized in that this reaction be at 50-450 ℃ temperature range, carrying out under the pressure of 0.05-20 crust and in the presence of as one or more metal acid-salts of the Mendeleev chart IV b of heterogeneous catalyst and V b family element.
2. according to the method for claim 1, it is characterized in that using by BET method surface-area being 0.1-500m
2One or more metal acid-salts of the Mendeleev chart IV b of/g and V b family element are as catalyzer, its consumption, under the situation of not exclusively operate continuously, weight with monohydroxy compound is benchmark, can be 0.5-100 weight %, perhaps under the situation of operate continuously fully, every gram catalyzer is per hour handled 0.1-20 gram monohydroxy compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4423863A DE4423863A1 (en) | 1994-07-07 | 1994-07-07 | Process for the preparation of aryl carbonates |
| DEP4423863.0 | 1994-07-07 |
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| Publication Number | Publication Date |
|---|---|
| CN1121065A CN1121065A (en) | 1996-04-24 |
| CN1073083C true CN1073083C (en) | 2001-10-17 |
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| CN95108160A Expired - Fee Related CN1073083C (en) | 1994-07-07 | 1995-07-06 | Process for the preparation of aryl carbonates |
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| Country | Link |
|---|---|
| US (1) | US5602271A (en) |
| EP (1) | EP0691326B1 (en) |
| JP (1) | JPH0827069A (en) |
| CN (1) | CN1073083C (en) |
| DE (2) | DE4423863A1 (en) |
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| DE19528298A1 (en) | 1995-08-02 | 1997-02-06 | Bayer Ag | Process for the continuous production of aryl carbonates |
| DE19606384A1 (en) | 1996-02-21 | 1997-08-28 | Bayer Ag | Process for the continuous production of aryl carbonates |
| DE19619224A1 (en) * | 1996-05-13 | 1997-11-20 | Bayer Ag | Process for the continuous production of aryl carbonates |
| US7151189B2 (en) | 2003-06-19 | 2006-12-19 | General Electric Company | Method and apparatus for waste stream recovery |
| JP5256687B2 (en) * | 2007-10-23 | 2013-08-07 | 三菱化学株式会社 | Method for producing diaryl carbonate |
| DE102008050828A1 (en) * | 2008-10-08 | 2010-04-15 | Bayer Materialscience Ag | Process for the preparation of diaryl carbonates |
| ES2643234T3 (en) | 2010-03-30 | 2017-11-21 | Covestro Deutschland Ag | Procedure for the preparation of diaryl carbonates and polycarbonates |
| US9175135B2 (en) | 2010-03-30 | 2015-11-03 | Bayer Materialscience Ag | Process for preparing diaryl carbonates and polycarbonates |
| EP2586767A1 (en) | 2011-10-25 | 2013-05-01 | Bayer MaterialScience AG | Method for manufacturing diaryl carbonates and polycarbonates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991006526A1 (en) * | 1989-10-30 | 1991-05-16 | The Dow Chemical Company | Process and catalyst for production of diaryl carbonates |
| US5239105A (en) * | 1992-01-30 | 1993-08-24 | The Dow Chemical Company | Catalytic formation of diarylcarbonates |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2362865A (en) * | 1941-07-18 | 1944-11-14 | Gen Chemical Corp | Manufacturie of aromatic esters |
| US2837555A (en) * | 1956-09-20 | 1958-06-03 | Dow Chemical Co | Preparation of carbonate esters |
| US3234263A (en) * | 1962-07-03 | 1966-02-08 | Union Carbide Corp | Process for preparing diaryl carbonates |
| US5252771A (en) * | 1991-05-28 | 1993-10-12 | The Dow Chemical Company | Aluminum trifluoride catalyst for production of diaryl carbonates |
| US5214017A (en) * | 1991-11-27 | 1993-05-25 | Sun Company, Inc. (R&M) | Solid-acid alkylation catalyst compositions for alkylation processes |
| DE4217818C1 (en) * | 1992-05-29 | 1993-09-16 | H.C. Starck Gmbh & Co Kg, 3380 Goslar, De |
-
1994
- 1994-07-07 DE DE4423863A patent/DE4423863A1/en not_active Withdrawn
-
1995
- 1995-06-16 TW TW084106154A patent/TW302358B/zh active
- 1995-06-23 US US08/494,111 patent/US5602271A/en not_active Expired - Fee Related
- 1995-06-26 EP EP95109939A patent/EP0691326B1/en not_active Expired - Lifetime
- 1995-06-26 DE DE59503906T patent/DE59503906D1/en not_active Expired - Fee Related
- 1995-06-26 ES ES95109939T patent/ES2124469T3/en not_active Expired - Lifetime
- 1995-06-30 JP JP7186526A patent/JPH0827069A/en active Pending
- 1995-07-06 CN CN95108160A patent/CN1073083C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991006526A1 (en) * | 1989-10-30 | 1991-05-16 | The Dow Chemical Company | Process and catalyst for production of diaryl carbonates |
| US5239105A (en) * | 1992-01-30 | 1993-08-24 | The Dow Chemical Company | Catalytic formation of diarylcarbonates |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59503906D1 (en) | 1998-11-19 |
| US5602271A (en) | 1997-02-11 |
| ES2124469T3 (en) | 1999-02-01 |
| EP0691326A1 (en) | 1996-01-10 |
| DE4423863A1 (en) | 1996-01-11 |
| JPH0827069A (en) | 1996-01-30 |
| CN1121065A (en) | 1996-04-24 |
| EP0691326B1 (en) | 1998-10-14 |
| TW302358B (en) | 1997-04-11 |
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